Graft copolymers of mixtures of acrylates and sulfonic acids on n-vinyl-3-morpholinone polymers, improved acrylonitrile compositions, and method of preparation



Jan. 8, 1963 s. A. MURDOCK ETAL. GRAF'T COPOLYMERS OF MIX TURES OF ACRYLATES AND SULF'ONIC ACIDS ON N-VINYL-3-MORPHOLINONE POLYMERS, IMPROVED AORYLONITRILE COMPOSITION, AND METHOD OF PREPARATION Filed Oct. 5, 1959 F i/omen /0us ar/ic/e compr/Lsea of an acry/onl/rf/epolymer Iva why a yr'a/f copolymer 0/ an aminoe/by/acry/afe or me/bacry/a fe monomergraft copo/ymergeo upon an N- virgy/dmorp/m/in one 0/ mer \s'u s/ra/e incorpor- /e o fbere/n.

INVENTORS. J/an/ey 19. Murdock C/yde M. Dav/Ls Farres/fl. lers United States Patent Ofifice 3,072,599 Patented Jan. 8, 1963 GRAFT COPOLYMERS OF MIXTURES OF ACRY- LATES AND SULFONIC ACIDS ON N-VINYL-3- MORPHOLINONE POLYMERS, IMPROVED AC- RYLONITRILE COMPOSITIONS, AND METHOD OF PREPARATION Stanley A. Murdoch, Rancho Cordova, Califi, Clyde W.

Davis, Williamsburg, Va., and Forrest A. Ehlers, Walnut Creek, Califi, assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware Filed Oct. 5, 1959, Ser. No. 844,319 18 Claims. (Cl. 26045.5)

The present invention resides in the general field of organic chemistry and contributes specifically to the polymer art, especially with respect to certain graft copolymers and fiber-forming polymer blends obtainable therewith. In this Way, the invention is pertinent to the man-made synthetic textile fiber industry.

The invention is particularly concerned with the graft copolym-eric products of mixtures of certain monomeric acrylates and certain monomeric organic sulfonic acid compounds that are graft copolymerized in admixture upon preformed substrate N-vinyl-3-morpholinone polymers (hereinafter referred to as VM polymers). Such graft copolymeric products have especial utility as dye-receptive, antistatic and stabilizing additaments for acrylonitrile polymer compositions which, advantageously, may be of the fiber-forming variety. The invention is also con cerned with the compositions that may be obtained by blending the graft copolymers with acrylonitrile polymers, as well as with shaped articles which have been fabricated therefrom, that have significantly enhanced properties and characteristics as regards improvements in and relating to enhanced dye-receptivity, minimized inherent propensity to accumulate electrostatic charges and an augmented natural stability to various deteriorating influences, including stability against becoming deleteriously influenced and degraded upon exposure to heat at elevated temperatures and light.

Within the scope and purview of the invention there is comprehended both the novel and utile graft copolymer and blended polymer compositions of the indicated varieties (as well as various shaped articles fabricated therefrom and comprised thereof) and advantageous methods for their preparation.

It is the main purpose and primary design of the present invention to provide and make available graft copolymers of certain acrylate monomers admixed with certain monomeric organic sulfonic acid compounds upon preformed VM polymer substrates, which graft copolymers are especially Well suited for being incorporated in acrylonitrile polymer compositions, particularly polyacrylonitrile, to serve in the indicated treble capacity of dye-assisting adjuvants, antistatic agents and stabilizing ingredients.

It is also a principal aim and concern of the invention to furnish acrylonitrile polymer compositions of the aboveindicated and hereinafter more fully delineated type and shaped articles therefrom that have, as intrinsic and distinguishing characteristics, excellent receptivity of and acceptability for any of a wide variety of dyestuffs; permanently imbued antistatic properties that are unusually good for and not commonly encountered in polymeric materials of the synthetic, essentially hydrophobic varieties of such substances; and efficacious natural stability to heat and light as well as to certain chemical conditions such as alkaline environments. The blended polymer compositions of the present invention which fulfill such ends and offer corollary advantages and benefits, as will hereinafter be manifest, are, in essence, comprised of an intimate and practically inseparable blend or alloy constitution of (A) an acrylonitrile polymer that contains in the polymer molecule at least about 80 weight percent of polymerized acrylonitrile, any balance being polymerized units of at least one other ethylenically unsaturated monomeric material that is copolymerizable with acrylonitrile, which acrylonitrile polymer preferably is of the fiber-forming variety and, most advantageously, is polyacrylonitrile and (B) a minor proportion of a beneficial graft copolymeric additament, also a subject of the invention, that functions and serves simultaneously in the treble capacity of a dye-assisting adjuvant, permanent antistatic agent and stabilizer and which is comprised of the graft copolymerized polymerization product of (a) a mixture of monomers consisting of 1) a monomeric Z-aminoethylacrylate or 2-aminoethylmethacrylate or their monomeric dimethyl or diethyl derivatives, as hereinafter more fully delineated, and (2) a monomeric organic sulfonic acid compound (including free acid compounds and ester or salt derivatives) that contains a substituent, reactive alkenyl, advantageously vinyl, group in its molecule; upon (12) a preformed VM polymer trunk or base substrate (as hereinafter more precisely delineated), particularly poly-N-vinyl-3-morpholinone (PVM).

The method of the invention by which such compositions may be made involves incorporating the minor proportion of the graft-copolymerized polymeric additament in and with the acrylonitrile polymer base by any of severalbeneficial techniques hereinafter more thoroughly defined, adapted to suitably accomplish the desired result. The graft copolymers are themselves made by graft copolymerizing the mixture of monomers upon the preformed VM polymer substrate, as hereinafter demonstrated.

Without being limited to or by the specific embodiments I and modes of operation set forth, the invention is exemplified in and by the following docent illustrations where in, unless otherwise indicated, all parts and percentages are to be taken on a weight basis.

ILLUSTRATION A A polymeric additament satisfactory for use in the practice of the present invention is prepared by charging into a suitable reaction vessel about 5.9 grams of ethylene sulfonic acid; about 9.0 grams of 2-aminoethylmethacrylate, hydrochloride (Z-AEMA, HCl); 59.5 grams of PVM having a relative viscosity in water at 25 C. of about 1.85 at a concentration of 1 gram of the water-soluble polymer in ml. of solution; grams of water and 0.2 gram of ammonium persulfate. The pH of the resulting mixture is about 1. The mixture is heated while being maintained in a nitrogen atmosphere, with continued agitation, for about 18 hours.

The resulting graft copolymer product is soluble in the aqueous polymerization mass. Conversion of the monomers to polymers is found to be about 95 percent to provide a graft copolymer product that contains about 84 percent of the PVM constituent upon which there is graft copolymerized about 6 percent of the polymerized ethylene sulfonic acid constituent and 10 percent of the polymerized Z-AEMA, HCl constituent.

'The dissolved graft copolymeric product is diluted with water to form a solution having about 2.5 percent of polymeric solids contained therein. This is used as an impregnating bath according to the procedure of the following illustration to obtain polyacrylonitrile fibers containing intimately incorporated therein about 3.4 percent, based on the weight of the final fiber product (o.w.f.), of the graft copolymeric additament. The graft copolymer-containing fiber product is found to have good dye-receptivity, quite satisfactory stability to heat and light, and an unusually slight or low propensity to accumulate charges of static electricity.

To determine the extent of its stability to ultraviolet light, the graft copolymer-containing fiber product is placed, under standard test conditions, in an Atlas F ade- The general procedure of the first illustration is followed to prepare two polymeric additaments with the followmg mixture that is duplicated to provide polymerization charges for each:

Sodium styrene sulfonate parts 20.1 2-aminoethylmethacrylate do 18.1 PVM (as in Illustration A) do 156.4 Water do 350 pH of mixture About 6 Ammonium persulfate parts 0.4

One of the charges is heated under a nitrogen blanket at 49 C., with continued agitation, for about 19 hours. Conversion of the monomeric constituents from the charge to polymeric product is about 95.9 percent. The polymeric product contains about 84 percent of PVM; about 8.5 percent of the polymerized sodium styrene sulfonate monomer; and about 7.5 percent of the polymerized Z-AEMA monomer. The polymer product is obtained as a stable white emulsion which consists essentially of a graft copolymer of the sodium styrene sulfonate and the 2-AEMA on PVM.

The pH of the other charge is adjusted to about 2 with hydrochloric acid and the reaction mass is then heated at the boiling point for about 1% hours during which time there is obtained a complete 100 percent conversion of the monomeric constituents to polymeric product. The polymeric product is obtained as a stable white emulsion in the aqueous medium and is found to consist of about 81 percent of the PVM; about percent of the polymerized sodium styrene sulfonate monomer; and about 9 percent of the polymerized Z-AEMA monomer. The polymeric product is likewise a graft copolymer of the sodium styrene sulfonate and 2-AEMA on PVM.

Polyacrylonitrile fibers containing about 8 percent of the first described of the above graft copolymers are prepared by impregnating, during their hot stretching, filamentary structures that are in aquagel condition after having been salt-spun. A boiling aqueous dispersion of the graft-copolymer that contains about 1 /2 percent graft copolymeric solids is employed as the hot-stretching and impregnating bath. The polyacrylonitrile aquagel fiber that is employed is obtained by extruding a spinning solution of fiber-forming polyacrylonitrile comprised of about 10 parts of the polymer dissolved in 90 parts of a 60 percent aqueous solution of zinc chloride through a spinnerette having 300 individual 6 mil diameter orifices into an aqueous coagulating bath that contains about 42 percent of dissolved zinc chloride to form a multiple filament tow. After being spun, the tow bundle of coagulated polyacrylonitrile aquagel fiber is washed substantially free from salt upon being withdrawn from the coagulating bath and then hot-stretched for orientation while being simultaneously impregnated with the graft copolymer to a total stretched length that is about thirteen times its original extruded length.

Following the hot-stretching impregnation, the aquagel fiber is irreversibly dried at 150 C. to destroy the waterhydrated structure and convert it to a finished fiber form. It is then heat set for five minutes at 150 C. The finally obtained 3 denier fiber product has a tenacity of about 3.5 grams per denier, an elongation of about 33 percent and a wet yield strength of about 0.85 gram per denier. The graft-copolymer-cont'aining acrylonitrile polymer fiber product has excellent natural stability to heat and light as well as against becoming degraded under the influence of aqueous alkaline media at pH levels as high as 10. It is found to be nearly free of propensity under normally humid conditions to accumulate charges of static electricity upon handling; being about commensurate with Viscose rayon fibers in this regard. As is widely appreciated, viscose rayon yarn and fibers are not considered to be afflicted to a troublesome degree with problems due to static.

The graft-copolymer-impregnated fiber product dyes well to deep and level shades of coloration with Calcodur Pink ZBL, a direct type of dyestuff (Colour Index Direct Red 75, formerly Colour Index 353) and Sevron Brilliant Red 4G, a basic dye formerly known as Basic Red 46 (Colour Index Basic Red 14).

The dyeing with Calcodur Pink 2BL is performed at the 4 percent level according to conventional procedure in which the fiber sample is maintained for about one hour at the boil in the dyebath which contains the dyestuff in an amount equal to about 4 percent of the weight of the fiber. The dyebath also contains sodium sulfate in an amount equal to about 15 percent of the weight of the fiber and has a bath-to-fiber weight ratio of about 30:1. After being dyed, the fiber is rinsed in water and dried for about 20 minutes at C.

The dye-receptivity of the Calcodur Pink ZBL-dyed fiber is then evaluated spectrophotometrically by measuring the amount of monochromatic light having a wave length of about 520 millimicrons from a standard source that is reflected from the dyed sample. A numerical value on an arbitrarily designated scale from zero to one hundred is thereby obtained. This value represents the relative comparison of the amount of light that is reflected from a standard white tile reflector that has a reflectance value of 316 by extrapolation from the 0100 scale. Lower reflectance values are an indication of better dyereceptivity in the fiber. For example, a reflectance value of about 20 or 25 to 50 or so for acrylonitrile polymer fibers dyed with 4 percent Calcodur Pink 28L is generally considered by those skilled in the art to be representative of a degree of dye-receptivity that readily meets or exceeds the most rigorous practical requirements and is ordinarily assured of receiving general commercial acceptance and approval.

The Calcodur Pink ZBL-dyed polyacrylonitrile fibers containing the above-described polymeric additament in accordance with the invention have a reflectance value of about 20. In contrast, ordinary unmodified polyacrylonitrile fibers of the same type generally have a reflectance value of about on the same numerical scale.

The antistatic properties of the graft-copolymer-containing fiber are then determined by measuring the electrical conductance of the fiber product at various humidities. As will be appreciated by those who are skilled in the art, the basis for such a test is that all fibers have a tendency to generate static electricity upon being handled. Only those that are possessed of sufficient electrical conductance to dissipate the charge as quickly as it forms are not hampered by the bothersome effects of static electricity. Thus a measure of the electrical conductance of a fiber is a good indication of its ability to dissipate static electricity. The conductivities of the various fiber samples tested are found by determining their electrical resistances. Resistance, of course, is the reciprocal quantity of conductivity. In order to permit various fiber samples to be compared on the common basis, the conductivities of the samples tested are actually measured as volume resistivities according to the following formula:

Volume resistivity (Resistance) (Cross-sectional area) Path length between electodes to which sample being tested is attached is scoured for /2 hour at the boil using about 1.0 percent .0;W.f. of an alkylphenoxypolyoxyethylene ethanol nonionic detergent and a 30:1 volumezfiber ratio of water. After being scoured, the fiber sample is washed thoroughly with water and dried. The actual resistivity of each sample is determined after the sample being tested is conditioned for seventy-two hours at the particular temperature and relative humidity conditions involved by tautly connecting a web-like sample of the yarn between two electrodes, each of which are 9 centimeters long spaced parallel 13 centimeters apart, and across which there is applied a 900 volt direct current potential. For purposes of comparison, the volume resistivity of cotton, wool and an unmodified polyacrylonitrile fiber (obtained in the same way as the graft-copolymer-containing fiber but without having the polymeric additament incorporated therein) are also tested in the indicated manner along with the graft-copolymer-containing fiber in accordance with the present invention.

The results are set forth in the following tabulation which indicates the volume resistivities at various relative humidities (R.H.) at 23 C. of each of the samples tested.

' 7 Table 1 VOLUME RESISTIVITIES OF VARIOUS FIBER SAMPLES COMPARED TO POLYACRYLONITRILE FIBERS IMPREG- NATED \VITH GRAFT COPOLYMERS OF SODIUM STY- RENE SULFONATE AND 2-AEMA, HCl ON PVM Volume Resistivity, Ohm-cmJ/cm.

Sample 32 percent 47 percent 58 percent 66 percent RH. RH. R.H. RH.

Graft-copolymer-impregnated polyacotton 6. 4X10 2. 7X10 3. 0x10 5. 4X10 Wool 5.0 10 2. 0X10" 1. 9X10 3. 3X10" Unmodified polyae- As is apparent from the foregoing, the graft copolymercontaining fiber sample, even after being severely scoured, has electrical conductance properties much superior to ordinary polyacrylonitrile fibers and only slightly poorer than cotton. At the same time, the physical properties of the graft copolymer-containing fiber are excellent, being about equal to those of the unmodified polyacrylonitrile fibers.

Equivalent results are obtained when the foregoing procedure is repeated excepting to impregnate the aquagel fiber with the copolymer additive prior to the stretchdrawing operation on the fiber.

ILLUSTRATION C Following the procedure of the preceding illustrations, a polymeric additament suitable for use in the practice of the present invention is made from the following charges:

2-sulfoethylacrylate, sodium salt (SEA, Na)

grams" 10.0 Z-aminoethylacrylate, hydrochloride (2-AEA, HCl) grams 72.8 PVM (Fikentscher K-value 57) do 72.8 Water milliliters 175 Ammonium persulfate gram 0.2

pregnating bath. A product containing about 5.051 percent of the graft copolymer additament therein, based on the weight of the fiber, is obtained. The modified fiber product dyes well, has low static characteristics and is exceptionally light stable. It withstands more than 240 hours of ultraviolet light exposure in an Atlas Fadeometer before there is any break in color.

ILLUSTRATION D The procedure of Illustration C" is repeated with the following charges:

Grams Sodium styrene sulfonate 10.05 Z-AEMA, HCl 9.05 PVM (Fikentscher K-value 45) 78.2 Ammonium persulfa-te 0.2

A white stable emulsion of the water-insolube graft copolymer product is obtained with high conversion of the monomeric ingredients to polymer product. The polymeric additament contains about 10 percent of polymerized styrene sulfonic acid; about 9 percent of polymerized Z-AEMA, HCl; and about 81 percent of the PVM. Polyacrylonitrile fibers are impregnated while in the aquagel condition with a 2.5 percent aqueous dispersion of the graft-copolymer product (pursuant to the general procedure set forth in Illustration B) to provide a graft-copolyrner-containing fiber having about 0.4 percent of the sodium styrene sulfonate constituent in the graft-copolymer present therein. The resulting graftcopolymer-containing fiber product has good physical properties, excellent heat, light and alkaline stability and dyes well to deep and level shades with Calcodur Pink ZBL, Calcocid Alizarine Violet, Amacel Scarlet BS and Sevron Brilliant Red 46. The graft copolymer-containing fiber withstands 240 hours of ultraviolet light exposure in the Atlas Fadeometer before there is any sign of color break.

ILLUSTRATION E The general procedure of Illustration D is repeated with a graft-copolymeric polymer additament prepared from thefollowing charge:

Conversion of the monomer to polymer product is high as a result of the polymerization which is conducted in the manner set forth in the foregoing illustration. The polymeric product contains about 11 percent of the polymerized sodium styrene sulfona-te; about 8 percent of the polymerized DMAEA; and about 81 percent of PVM.

Polyacrylonitrile aquagel fibers are impregnated with a 2.5 percent aqueous solution of the water-soluble graft copolymer product according to the above-indicated pro cedure so that the graft copolymer-containing fibers has a sufiicient quantity of the polymeric additament incorporated therein to have about a 0.5 percent content of the polymerized sodium styrene sulfonate constituent of the graft copolymer. The resulting modified fiber product has excellent physical properties, good dyeability and satisfactory stability. Its static characteristics are about commensurate with those of cotton.

ILLUSTRATION F 7 About 21 grams of sodium styrene sulfonate, 16 grams of diethylaminoethylmethacrylate (DEAEMA), 99 grams of PVM having a Fikentscher K-value of about 57, 600 ml. of water and 0.8 gram of ammonium persulfate are charged into a reaction vessel and polymerized for 16 hoursat 50 C. under a nitrogen atmosphere, with continued agitation, after the pH of the reaction mass is initially adjusted to about 3 with hydrochloric acid. Conversion to a clear, colorless, water-soluble graft copolymer product is nearly complete. Excellent results are achieved when the polymer product is incorporated in acrylonitrile polymer fibers as a dye-receptive, antistatic, stabilizing adjuvant.

ILLUSTRATION G A graft copolymerized, dye-receptive, antistatic, stabilizing adjuvant is manufactured by graft-copolymerization of the following charge under a nitrogen atmosphere with continued agitation for 18 hours at 50 C. after initial adjusting of the pH of the charge to about 3 with hydrochloric acid:

The resulting graft-copolymer is found to contain about 12 percent of the polymerized SEA, Na; about 8 percent of the polymerized DMAEA; and about 80 percent of the PVM. Polyacrylonitrile fibers in aquagel form are impregnated in the above-described manner with a 2.5 percent aqueuos solution of the indicated copolymer product so that the finally obtained, dried, modified acrylonitrile polymer fibers contain about 0.3 percent of the polymerized SEA, Na constituent of the polymeric additament. The resulting fiber product dyes well, has very low static characteristics, and is exceptionally stable to light, heat and alkalinity. It withstands 240 hours of continuous ultraviolet light exposure in an Atlas Fadeometer before any color break can be denoted.

ILLUSTRATION H About 1.66 grams of Z-AEMA, HCl; 2.01 grams of N-acryloyl taurine, sodium salt (the nomenclature taurine being commonly employed for the designation of Z-aminoethanesulfonic acid); 8.55 grams of PVM having a Fikentscher K-value of about 57; 48.45 grams of water and 0.04 gram of potassium sulfate are mixed together and the pH adjusted to about 3 with HCl to provide a polymerization mixture. The mixture is heated f r 16 hours, with continued agitation, under a nitrogen atmosphere at about 50 C. during which time conversion of the monomers to a water-insoluble graft copolymer product is substantially complete. The product is obtained in an aqueous emulsion. When it is impregnated in polyacrylonitrile aquagel fibers according to the foregoing procedures so as to obtain a modified polyacrylonitrile fiber product, the resulting fiber product has excellent dye-receptivity, low static characteristics and good stability to light, heat and alkaline conditions.

ILLUSTRATION I Excellent results are obtained with a polymeric dye-receptive, antistatic, stabilizing additament for acrylonitrile polymer fibers with a graft-copolymer prepared in essential accordance with the method set forth in Illustration H using the following charge:

Grams Acryloyl taurine, sodium salt 2.01 DMAEA 1.71 PVM (Fikentscher K-value 45) 8.69 Water 49.60 Potassium per'sulfate 0.04

net and fiber-forming acrylonitrile polymer in a spinning compositon or dope prior to its extrusion into filamentary products by either wet-spinning or dry-spinning techniques. In such instances, incidentally, it may be desirable (in order to secure optimum benefit in the practice of the invention) to employ relatively larger quantities of the graft copolymeric additament than when surface impregnation is performed so that the presence of effective quantities of the additament at or near the surface of the article is assured.

Excellent results may also be obtained when other VM polymer substrates are employed for the graft copolymer additaments, such as copolymers of VM with N-vinyl-Z-pyrrolidone; N-vinyl caprolactam; N-vinyl-S- methyl-Z-pyrrolidone; N-vinyl piperidone; and other vinyl lactam monomers; N-vinyl-Z-oxazolidinone; N-vinyl-S- methyl-Z-oxazolidinone; N vinyl-5-ethyl-2-oxazolidinone N-vinyl-Z-oxazinidinone; and other N-vinyl cyclic carbamate monomers; and so forth (within the compositional ranges detailed below; and when other arcylonitrile polymer bases of the copolymeric variety other than polyacrylonitrile are modified with the additaments.

The graft copolymeric additaments that are employed in the practice of the invention, as is indicated in the foregoing, are graft copolymerized products of (a) mixtures of monomers consisting of (1) 2-aminoethacrylates and/ or Z-aminomethacrylates having the formula RzNCzHr-O 3-(il=CHt (I) wherein each R is independently selected from the group consisting of hydrogen, methyl and ethyl and G is selected from the group consisting of hydrogen and methyl (typical examples of which are 2-arninoethylacrylate; 2- aminoethylmethacrylate; methyl 2 aminoethylacrylate; methyl-2-aminoethylmethacrylate; dimethyl-2-aminoethylacrylate; dimethyl-2 aminoethylmethacrylate; ethyl 2- aminoethylacrylate; ethyl-2-amincethylmethacrylate; diethyl-2-aminoethylacrylate; diethyl 2 aminoethylmethacrylate; methyl ethyl-2-arninoethylacrylate; and methyl ethyl-2-aminoethylmethacrylate), and (2) alkenyl groupcontaining organic sulfonic acids and derivatives thereof that are selected from the group of such compounds consisting of those represented by the formulae (including mixtures thereof):

CHz=C (CH2) ;,SO;X

(Aromatic organic sulfonic acid compounds) CH2: CH- CH2) mSO3X (Alkenyl organic sult'onic acid compounds) CHg=CCOO--(CHz)nSO;X

(Sulfoalkylacrylate organic sulfonic acid compounds) CH2=CC ONE-(CH1) n-SO;X

& (V) (Acryloyl taurine homolog compounds) (Allyl taurine liomolog compounds) all wherein X is hydrogen, an aliphatic hydrocarbon radical containing from 1 to 4 carbon atoms or an alkali metal ion; Y is hydrogen, chlorine or bromine; R is methyl or ethyl; Z is hydrogen or methyl; in has a numerical value in whole number increments from 0 to 2; n has a numerical value of 1 or 2; p is 0 or 1; and m is an integer from 1 to 4; upon (b) preformed VM polymer substrates, particularly PVM.

Besides those specifically illustrated, other monomeric organic sulfonic acid compounds may also be utilized for the preparation of the graft copolymeric additaments of the present invention, such by way of illustration, as those which are set forth in the disclosure of United States Letters Patent No. 2,527,300. In addition to the sulfonic acid monomers specifically described in the foregoing examples, others that may advantageously be employed in the practice of the present invention include such organic sulfonic acids as 2-propene sulfonic acid; sodium para-vinylbenzene sulfonate; 2- and/ or 3-sulfopropyl acrylate; 2-sulfoacrylic acid; sodium vinyl toluene sulfonate; potassium ortho-chloro-styrene sulfonate; 2-hydroxy-3- sulfopropyl acrylate, sodium salt; sodium 3-allyloxy-2- hydroxypropane sulfonate; 4-sulfophenyl acrylate, sodium salt; N-allyl imino di-(Z-ethane sulfonic acid); and the like. Still others are set forth in the subsequent Appendix annexed hereto.

The N-vinyl-3-morpholinone polymers that are utilized as preformed substrates in the preparation of the graft copolymeric additaments of the present invention have, as an essential constituent of their polymeric structure,

characterizing proportions of the recurring group:

As has been indicated, copolymers of N-vinyl-3-morpholinone may also be employed. Thus, copolymers of N-vinyl-3-morpholinone with various homologous alkyl ring-substituted N-vinyl-3-morpholinone monomers may be utilized, such as copolymers of N-vinyl-3-morpholinone with N-Vinyl-S-methyl-3-morpholinone, N-vinyl-5-ethyl-3- morpholinone, and the like. Copolymers of N-vinyl-3- morpholinone with various N-vinyl lactam polymers, such as N-vinyl pyrrolidone, N-vinyl-piperidone, N-vinylcaprolactam, N-vinyl-S-methyI-Z-pyrrolidone and the like may also be prepared. Advantages are also achieved with copolymers of N-vinyl-3-morpholinone and various of the N-vinyl-2-oxazolidinone monomers, such as N- vinyl-Z-oxazolidinone, N-vinyl-S-methyl-2-oxazolidinone,

.N-vinyl-S-ethyl-2-oxazolidinone, N-vinyl-2-0Xaz0lidinone,

and so forth.

Advantageously, the N-Vinyl-3-m0rpholinone polymer that is used in the manufacture of the graft copolymer product has a Fikentscher K-value between about 5-10 and about 100 and, more advantageously, between about 2030 and 60.

Beneficially, as mentioned, the N-vinyl-3-morpholinone polymer that is utilized is a water-soluble material. In cases where N-vinyl-3-morpholinone copolymers are employed that tend to Water-insolubility with decreasing proportions of N-vinyl-B-morpholinone in the copolymer molecule (as is the case with copolymers of N-vinyl-3- morpholinone and N-vinyl-S-methyl-Z-oxazolidinone), it is generally most desirable for the copolymer to maintain at least about 40 weight percent of the N-vinyl-3-morpholinone polymerized therein. This avoids working with a product that may have a cloud (or precipitation) point in water or other aqueous solution beneath the boil.

These N-vinyl-B-morpholinone polymers and their preparation are discussed in US. Patents 2,952,668, filed April 16, 1958; 2,946,772, filed February 27, 1958; and 2,948,708, filed April 3, 1958; and in the co-pending ap plication for US. Patent having Serial No. 692,587, now U.S. 2,987,509, filed October 28, 1957, and entitled N- Vinyl-3-Morpholinone Compounds.

The graft copolymeric additaments that are prepared and employed in the practice of the invention may either be water-soluble or water-insoluble products. In either event, they are generally found to be readily dispersible in aqueous media by either dissolution therein or uniform dispersion throughout the medium to provide a usable product for impregnating purposes. The graft copolymers may generally be prepared by conventional methods of polymerization, including those which have been demonstrated in the foregoing exemplifying illustrations. 'In addition to the usual catalysts, including persulfates, organic and inorganic peroxides and azo type catalysts, the graft-copolymers may oftentimes be polymerized under the influence of high energy radiation such as by means of X-rays and the like, or simply by heating and evaporating the monomer-containing polymerization mixture. The graft-copolymers may be prepared in both aqueous and organic solvent vehicles, using temperatures for the desired polymerization that may vary from about room temperature to the boiling point of the polymerization mixture. It is ordinarily satisfactory to conduct the reaction at a temperature of about 50 to or 100 C. Usually depending upon the specific factors that may be involved, the copolymerization may be accomplished satisfactorily within a time period of about 10 to 60 hours.

The compositions of the graft copolymerized polymeric additaments can vary within rather wide limits. Advantageously, the content of the preformed VM polymer substrate upon which the monomeric constituents are graft copolymerized is between about 10 and about percent, more advantageously between about 20 and about 80 percent, of the weight of the graft copolymerized product with the content of either monomeric constituent being between about 10 and about 90, more advantageously from about 30 to about 70, mole percent of the polymerized monomer substituents in the graft copolymerized product. It may frequently be desirable for the monomeric constituents that are polymerized to be employed in nearly equivalent or about commensurate or equal molar proportions in the preparation of the graft copolymeric polymeric additament and for the quantity of the preformed VM polymer substrate to be at least half of the constitution of the graft copolymer product.

The'polymerization system that is employed for the preparation of the copolymers employed in the present invention may consist of as much as 50 percent by weight of the monomers and preformed VM polymer substrate to be graft-copolymerized in the aqueous medium. The amount of monomeric and polymeric material that is .provided in the polymerization system may be influenced somewhat by the manner in which it is intended to incorporate the product in the synthetic polymer compositions in order to provide the compositions of the invention.

If, for example, it is intended. to incorporate the graftcopolymer products by blending into a fiber-forming composition prior to its fabrication into shaped articles, the copolymerization system may, if desired, contain about equal proportions by Weight of the charged materials and the polymerization medium which preferably is miscible with and tolerable in the spinning solution solvent being used. In case the graft-copolymer product is obtained as a gel, it may still be easily dispersed, after being dried and isolated. from unreacted monomer, in order to be directly incorporated in the fiber-forming composition.

If the incorporation of the polymeric additament in a fiber-forming composition is to be achieved by impregnation therewith of an already-formed shaped article of the composition, it may be desirable to eifect the polymerization so as to directly form the polymerization system'as a suitable applicating emulsion or suspension or as a solution of the graft-copolymeric product depending on its particular solubility characteristics. For such purposes, the polymerization system may be prepared to contain as little as 210 percent by weight of the graft-copolymerizing ingredients. Preferably, such a polymerization may be conducted under the influence of vigorous agitation, especially to facilitate preparation of an emulsified or thoroughly dispersed product when a water-insoluble graft-copolymer is being made. It may also be beneficial under such circumstances to incorporate a dispersant or emulsifying agent in the polymerization system to facili tate obtaining a stable and homogenous emulsified product. Such a method for preparing the graft-copolymeric additaments that are employed in the present invention may be especially appropriate when they are are intended to be applied to acrylonitrile polymer fibers and the like that are derived from aquagels in the course of their manufacture, such as the acrylonitrile polymer fibers that are wet spun from aqueous saline solutions of the fiber-forming polymer.

In such instance, as has been demonstrated, the graftcopolymeric additaments may be impregnated from solution or suspension into the fiber while it is in a swollen or gel condition. as an acrylonitrile polymer fiber in an aquagel condition, in order to obtain the desired graft-copolymer-containing product.

In this connection, when it is desired to blend the polymeric additament in a synthetic polymer fiber-forming solution prior to its extrusion, such as an aqueous saline acrylonitrile polymer solution, the graft-copolymer may be physically reduced by comminution to a sutliciently fine state to permit its dispersion in spinnable condition throughout the blended spinning solution in the event that it is otherwise insoluble in the solvent. While this may be accomplished by diverse techniques, it is generally advantageous to comminute the polymeric additament in the presence of the non-dissolving solvent, such as an aqueous saline polyacrylonitrile solvent, to form a stable suspension that may be more conveniently blended with the spinning solution of the synthetic polymer, such as an aqueous saline acrylonitrile polymer spinning solution. Thus, if the aqueous, saline polyacrylonitrile solvent that is being employed in an aqueous solution of zinc chloride or its equivalent that contains at least about 55 percent and preferably about 60 percent by weight of dissolved zinc chloride, it may be advantageous to comminute the polymeric additament while it is in a mixture with the saline solvent solution that contains between about and percent by weight of the graft-copolymer. Analogous procedures may be employed when other solvents are involved. Ball or rod mills or other attrition apparatus may be employed beneficially for the comminution. It is generally beneficial under such circumstances to avoid the use of balls or rods that are made of metal since they may contaminate the product, especially when aqueous saline solvents are utilized. Porcelain or other ceramic parts may usually be employed with advantage. A stable suspension of an insoluble graft-copolymeric additament in the acrylonitrile polymer solvent that is suitable for blending in the spinning solution of the acrylonitrile polymer to provide a spinnable composition may usually be obtained by milling the mixture of polymeric additament and solvent for an extended period that may exceed 100 hours. The suspension that is thereby obtained may then be directly blended in the proper proportions with the acrylonitrile polymer spinning solution to provide a composition in accordance with the present invention. Of course, many of the graft copolymer products of the invention are directly soluble in such spinning solutions.

If desired, the graft-copolymer-containing acrylonitrile polymer compositions may comprise as much as 20 or more weight percent of the graft-copolymeric additament, based on the weight of the composition. Usually, however, suitable proportions and characteristics and better fiber-forming properties in a given composition may be achieved when lesser proportions of the polymeric additament are incorporated therein. An appreciable improvement in dye-receptivity, antistatic properties and stability may frequently be obtained when a quantity of the graftoopolymeric additament that is less than 0.5 weight percent is employed. Advantageously, an amount between about 2 and weight percent of the polymeric additament may thus be utilized in the composition. Greater advantages may often accrue when the amount of the polymeric additament that is incorporated in the composition is not in excess of about 10 weight percent, based on the weight of the composition.

As has been indicated, the graft-copolymeric additaments may be incorporated in the acrylonitrile polymer compositions according to various techniques. Thus, for example, the additament and the acrylonitrile polymer may be directly blended in order to provide the composition which, incidentally, may be used for any desired fabrication purpose in addition to fiber-forming and the like. Beneficially, the polymers may be comminuted, either separately or in combination, before being intimately blended together by mechanical or other means. The blended polymers may be prepared into suitable fiberforming systems by dispersing or dissolving them in a suitable liquid medium. Or, the compositions may be provided in fiber-forming system by sequentially dispersing or dissolving the polymers in any desired order in a suitable medium, as by incorporating the polymeric additament in a prepared acrylonitrile polymer spinning solution, dope or the like. As is obvious, the graft-copolymeric additaments employed in the practice of the present invention are frequently found to be insoluble. Despite this fact, they are, as has been indicated, readily dispersible in most solvents.

As is evident from the illustrative examples heretofore included, a highly advantageous technique for providing the compositions, particularly when acrylonitrile polymer fiber products are involved, is to apply or impregnate the polymeric additament in a known manner from an aqueous solution or dispersion thereof to a shaped acrylonitrile polymer article that is in an aquagel condition. Thus, an acrylonitrile polymer filamentary article that has been spun from an aqueous saline spinning solution may be conveniently passed, after its coagulation and while it is in an aquagel condition, through a water bath containing a dispersed graft-copolymeric additament in order to impregnate the filament with the graft-copolymer and provide a composition and an article in accordance with the invention.

In addition, in situ polymerization techniques may be employed to provide the graft-copolymeric additament in the fiber product. Thus, the compositions may be made by impregnating an acrylonitrile polymer, such as a shaped article in aquagel form or other swollen condition, with the unpolymerized monomers and the preformed VM polymer substrate and graft-copolymerizing them therein by means of radiation, dry heat or steam with or without other catalyzing influence.

The compositions of the invention may advantageously be utilized in or with fiber-forming systems of any desired type in order to provide fibers and the like according to procedures and techniques that are conventionally employed for such purposes in the preparation of fibers and such related shaped articles as filaments, strands, yarns, tows, threads, cords and other funicular structures, ribbons, tapes, films, foils, sheets and the like which may be manufactured from synthetic polymeric materials. It is frequently desirable to employ concentrated solutions of salts or mixtures of salts as the dispersing or dissolving media for such purposes. Such solutions may, as has been indicated, contain at least about 55 weight percent, based on solution weight, of zinc chloride or other known saline solvents for the polymer. Acrylonitrile polymer fiber products that are spun from saline fiberforming systems may, by way of further illustration, be coagulated in more dilute saline solutions of a like or similar nature and may then be processed after coagulation according to conventional techniques of washing, stretching, drying, finishing and the like with the modification of the present invention being accomplished prior or subsequent to the spinning as may be desired and suitable in particular instances.

The acrylonitrile polymer fiber products in accordance with the present invention (one of which is schematically illustrated in the sole FIGURE of the accompanying drawing) have excellent physical properties and other desirable characteristics for a textile material and have a high capacity for and are readily and satisfactorily dyeable to deep and level shades with any of a wide variety of dyestuiis. For example, they may be easily and success fully dyed according to conventional procedures using acid, vat, acetate, direct, naphthol and sulfur dyes.

Such dyestuffs, by way of didactic illustration, as Calcocid Alizarine Violet (Colour Index 61710, formerly Colour Index 1080), Sulfanthrene Red 3B (Colour Index Vat Violet 2), Amacel Scarlet GB (Colour Index Direct Red 1 also known as Amacel Scarlet BS, and having American Prototype Number 244), Calcodur Pink 2BL (Colour Index 353, also more recently, Colour Index Direct Red 75), Naphthol ASMX (Colour Index 35527), Fast Red TRN Salt (Colour Index Azoic Diazo Component 11), and Immedial Bordeaux G (Colour Index Sulfur Brown 12) may advantageously be employed for such purposes.

Other dyestuiIs, by Way of further illustration, that may be utilized beneficially on the graft copolymer-containing acrylonitrile polymer blended fiber products of the invention include such direct cotton dyes as Chlorantine Fast Green SBLL (Colour Index Direct Green 27), Chlorantine Fast Red 7B (Colour Index Direct Red 81), Pontamie Green GX Cone. 125 percent (Colour Index Direct Green 6), Calcomine Black EXN Cone. (Colour Index Direct Back 38), Niagara Blue NR (Colour Index Direct Blue 151) and Erie Fast Scarlet 4BA (Colour Index Direct Red 24); such acid dyes as Anthraquinone Green GN (Colour Index Acid Green 25), Sulfonine Brown 2R (Colour Index Acid Orange 51), Sulfonine Yellow 2G (Colour Index Acid Yellow 40), Xylene Milling Black 2B (Colour Index Acid Black 26A), Xylene Milling Blue FF (Coour Index Acid Blue 61), Xylene Fast Rubine 3GP PAT (Colour Index Acid Red 57) Calcocid Navy Blue R Conc. (Colour Index Acid Blue 120), Calcocid Fast Blue BL (Colour Index Fast Blue 59), Calcocid Milling Red 3R (Colour Index Acid Red 151), Alizarine Levelling Blue 2R (Colour Index Acid Blue 51), Amaoid Azo Yellow G Extra (Colour Index Acid Yellow 63); such mordant-acid dyes as Alizarine Light Green GS (Colour Index Acid Green 25); such basic dyesas Brilliant -Green Crystals (Colour Index Basic Green 1), and Rhodamine B Extra S (Colour Index .V at Blue 35); such vat dyestutfs as Midland Vat Blue R Powder (Colour Index Vat Blue 35), Sulfanthrene Brown G Paste (Colour Index Vat Brown 5), Sulfanthrene Blue 2B Dbl. Paste (Co our Index Vat Blue 5), and Sulfan- ,threne Red 3B Paste (Colour Index Vat Violet 2); various soluble vat dyestuffs; such acetate dyes as Celliton Fast Brown 3RA Extra CF (Colour Index Dispersed Orange 5), Celliton Fast Rubine BA CF (Colour Index Dispersed Red 13), Artisii Direct Red 3B? and Celanthrene Red 3BN Conc. (both Colour Index Dispersed Red 15), Celanthrene Pure Blue BRS 400 percent (Colour Index Dispersed Blue 1) and Acetamine Yellow N (Colour Index Dispersed Yellow 32); B-Naphthol 2- chloro-4-nitroaniline, an azoic dye; such sulfur dyes as Katigen Brilliant Blue GGS High Conc. (Colour Index Sulf. Blue 9) and Indo Carbon CLGS (Colour Index Sult'. Blue 6); and various premetallized dyestuffs. I

The dyed products are generally lightfast and stable to heat and are well imbued with a resistance to crocking. In addition, the dyed products exhibit good washfastness and retain the dye-assisting polymeric additament in a substantially permanent manner despite repeated cleaning treatments.

Appendix Representative of the various monomeric organic sul- 14 tonic acid compounds that may be employed satisfactorily in the practice of the present invention are those set forth in the following listing, wherein they are grouped according to the several designated types. The list, by no means exhaustive, includes species not mentioned in the foregoing.

Aromatic alkenyl-containing sulfonic acid compounds (Formula II) Para-styrene sulfonic acid Ortho-styrene sulfonic acid Para-isopropenyl benzene sulfonic acid Para-vinyl benzyl sulfonic acid Ortho-isopropenyl benzyl sulfonic acid Sodium para-styrene sulfonate Potassium ortho-styrene sulfonate Methyl para-styrene sulfonate Ethyl para-vinyl benzyl sulfonate 'Ortho vinyl benzene sulfonic acid Isopropyl ortho-isopropenyl benzene sulfonate n-Butyl ortho-styrene sulfonate Tertiary butyl para-styrene sulfonate 2-chloro-4-vinyl benzene sulfonic acid 4-bromo-2-isopropenyl benzene sulfonic acid 3-vinyl toluene 6-sulfonic acid, sodium salt 2-ethyl-4-vinyl-benzene sulfonic acid 2,3-dichloro-4-vinyl benzene sulfonic acid 2,3,5-tribromo-4-vinyl benzene sulfonic acid 2-chloro-3-vinyl-toluene-6-sulfonic acid 2,3-diethyl-4-vinyl-benzyl sulfonate, sodium salt Alkenyl sulfonic acid compounds (Formula III) Ethylene sulfonic acid Sodium ethylene sulfonate Potassium ethylene sulfonate Methyl ethylene sulfonate Isopropyl ethylene sulfonate l-propene 3-sulfonic acid l-propene l-sulfonic acid, sodium salt l-propene 2-sulfonic acid, ethyl ester l-butylene 4-sulfonic acid, n-butyl ester l-butylene 3-sulfonic acid Tertiary butylene sulfonic acid Sulfoalkylacrylate compounds (Formula IV) Sulfomethylacrylate 2-sulfoethylacrylate Sulfomethylmethacrylate, sodium salt 2-sulfoethylmethacrylate, methyl ester 2-sulfoethylmethacrylate, potassium salt Acryloyl taurine and homolog compounds (Formula V) N-acryloyl taurine N-acryloyl taurine, sodium salt N-methacryloyl taurine, methyl ester N-rnethacryloyl taurine, potassium salt N-acryloyl taurine, ethyl ester N-acryloyl-aminomethane sulfonic acid N-methacryloyl-aminomethane sulfonic acid, sodium salt , Methyl N-methacryloyl-aminomethane sulfonate Allyl taurine and homolog compounds (Formula VI) Allyl taurine Allyl taurine, sodium salt Allyl taurine, potassium salt Methallyl taurine Methallyl taurine, methyl ester Methallyl taurine, isopropyl ester N-allyl-aminomethane sulfonic acid Sodium N-allyl-aminomethane sulfonate Lithium N-methallyl-aminomethane sulfonate n-Butyl N-allyl-aminomethane sulfonate What is claimed is:

1. Composition comprising between about and about 99.5 weight percent, based on composition weight, of (A) a polymerized ethylenically unsaturated monomeric material containing at least about 80 weight percent of polymerized acrylonitrile, and (B) between about 20 and about 0.5 weight percent, based on composition weight, of a graft copolymer of (a) from about 10 to about 90 weight percent, based on graft copolymer weight, of a mixture of monomers consisting of (1) from about 10 to about 90 mole percent of an acrylate monomer of the formula:

CHz=C (CH2) r-S 03X m CH =CH-( CH -S X (III) (3112:0-00 0- 0H2) n-so,x

i (IV) CHFC-C ONE-(CHDr-SOaX (v) and CH:=CCHzNH-(CHt)nS0aX wherein X is selected from the group consisting of hydrogen aliphatic hydrocarbon radicals containing from 1 to about 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl; m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; with (b) from about 90 to about weight percent, based on graft-copolymer weight, of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N- vinyl-3-morpholinone and up to 90 weight percent of another polymerized N-vinylheterocyclic compound which compound is copolymerizable with N-vinyl-3-morpholinone.

2. The composition of claim 1, wherein the graft copolymer is styrene sulfonic acid and 2-aminoethylmethacrylate on poly-N-vinyl-3-morpho'linone.

3. The composition of claim 1, wherein the graft copolymer is 2-sulfoethylacrylate and Z-aminoethylmethacrylate on poly-N-vinyl-3-morpholinone.

4. The composition of claim 1, wherein the graft copolymer is styrene sulfonic acid and dimethylaminoethylacrylate on poly-N-vinyl-3-morpholinone.

5. The composition of claim 1, wherein the graft copolymer is acryloyl taurine and dimethylaminoethylacrylate on poly-N-vinyl-3-morpho1inone.

6. The composition of claim 1, wherein the graft copolymer is styrene sulfonic acid and diethylaminoethylmethacrylate on poly-N-vinyl-3-morpholinone.

7. The composition of claim 1, wherein the acrylonitrile polymer is polyacrylonitrile.

8. The composition of claim 1 in a solvent for polyacrylonitrile.

9. A filamentary shaped article having the composition as set forth in claim 1.

10. Method for the preparation of a dye-receptive, antistatic, stable to light and heat, synthetic, hydrophobic polymer composition which comprises physically blending together between about 0.5 and about 20 weight percent, based on composition weight, of (B) a graft co- 16 polymer of from about 10 to about 90 percent by Weight, based on graft copolymer weight, of (a) a mixture of monomers consisting (1) from about 1'0 to about 90 mole percent of an acrylate monomer of the formula:

G RzNCzH4O( 3=CHz (I) wherein each R is independently selected from the group consisting of hydrogen, methyl and ethyl and G is selected from the group consisting of hydrogen and methyl; and (2) from about 90 to about 10 mole percent of an alkenyl-group containing organic sulfonic acid compound selected from the group consisting of those having the formulae:

wherein X is selected from the group consisting of hydrogen aliphatic hydrocarbon radicals containing from 1 to about 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl; m is an integer from O to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; and (b) from about 90 to about 10 weight percent, based on graft copolymer weight, of a polymerized monoethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to 90 weight percent of another polymerized N-vinyl heterocyclic compound which compound is copolymerizable with N-vinyl-3-morpholinone and (A) between about and about 99.5 weight percent, based on composition weight, of a polymerized ethylenically unsaturated monomeric material containing at least about 80 weight percent of polymerized acrylonitrile.

11. Method for the preparation of a dye-receptive, antistatic, stable to light and heat, synthetic, hydrophobic polymer composition which comprises immersing an aquagel of a polymerized ethylenically unsaturated monomeric material containing at least about 80 weight percent of polymerized acrylonitrile in the form of a shaped article into an aqueous dispersion of a graft copolymer of (a) from about 10 to about weight percent, based on graft copolymer weight, of a mixture of monomers consisting of (1) from about 10 to about 90 mole percent of an acrylate monomer of the formula:

wherein each R is independently selected from the group consisting of hydrogen, methyl and ethyl and G is selected from the group consisting of hydrogen and methyl; and (2) from about 90 to about 10 mole percent of at least one alkenyl-containing organic sulfonic acid com- 17 pound selected from the group consisting of those of the formulae:

Z (V wherein X is selected from the group consisting of hydrogen aliphatic hydrocarbon radicals containing from 1 to about 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl; m is an integer from to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; and (b), between about 90 and about weight percent, based on composition weight, of a polymerized ethylenically unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to 90 weight percent of another polymerized N-vinyl heterocyclic compound which compound is copolymerizable with N-vinyl-3-morpholinone until between about 0.5 and about 20 weight percent of said graft copolymer, based on resulting dry composition weight, is incorporated in said aquagel; and drying said graft-copolymer containing aquagel to convert it from the aquagel condition to a finished shaped article form.

12. The method of claim 11, wherein said acrylonitrile polymer is polyacrylonitrile.

13. The method of claim 11, wherein said N-vinyl-3- morpholinone polymer is poly-N-vinyl-3morpholinone.

14. A graft copolymer of between about 10 and about 90 weight percent of (a) a mixture of monomers consisting of (1) from about 10 to about 90 mole percent of an acrylate monomer of the formula:

wherein each R is independently selected from the group consisting of hydrogen, methyl and ethyl and G is selected from the group consisting of hydrogen and methyl; and (2) from about 90 to about 10 mole percent of an alkenyl-group containing organic sulfonic acid compound selected from the group of those represented by the formulae:

18 wherein X is selected from the group consisting of hydrogen aliphatic hydrocarbon radicals containing from 1 to about 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl; m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4; and (b) from about 90 to about 10 weight percent of a polymerized monoethylenicallyunsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3- morpholinone and up to 90 weight percent of another polymerized N-vinyl heterocyclic compound which compound is copolymerizable with N-vinyl-3-morpho1inone.

15. The graft copolymer of claim 14, containing, in polymerized form, from about 20 to about weight percent of about equal molar proportions of said mixture of monomers as graft copolymerized substituents upon from about 80 to about 20 weight percent of said N-vinyl- 3-morpholinone polymer substrate.

16. The graft copolymer of claim 14, wherein said mixture of monomers consists of (1) from about 30 to about 70 mole percent of said acrylate monomer of said Formula I and (2) from about 70 to about 30 mole percent of said monomeric organic sulfonic acid compound selected from the group consisting of those represented by said Formulae II, III, IV, V and VI.

17. The graft copolymer of claim 14, wherein said N- vinyl-3-morpholinone polymer is poly-N-vinyl-3-morpholinone.

18. Method for the preparation of a graft copolymer which comprises polymerizing in the presence of about to about 10 weight percent, based on resulting graft copolymer Weight, of a polymerized monoethylenica'lly unsaturated monomeric material containing at least about 10 weight percent of polymerized N-vinyl-3-morpholinone and up to 90 weight percent of another polymerized N- vinyl heterocyclic compound which compound is copolymerizable with N-vinyl-3-morpholinone, between about 10 and about 90 weight percent of a mixture of monomers consisting of (a) from about 10 to about 90 mole percent of an acrylate monomer of the formula:

II I RzNCzHr-O oo=onl (I) wherein each R is independently selected from the group consisting of hydrogen, methyl and ethyl and G is selected from the group consisting of hydrogen and methyl; and (b) from about 90 to about 10 mole percent of a monomeric organic sulfonic acid compound selected from the group consisting of those represented by the formulae:

wherein X is selected from the group consisting of hydrogen aliphatic hydrocarbon radicals containing from 1 to about 4 carbon atoms and alkali metals; Y is selected from the group consisting of hydrogen, chlorine and 19 bromine; R is selected from the group consisting of methyl and ethyl; Z is selected from the group consisting of hydrogen and methyl; m is an integer from 0 to 2; n is an integer from 1 to 2; p is an integer from 0 to 1; and r is an integer from 1 to 4.

References Cited in the file of this patent UNITED STATES PATENTS 

1. COMPOSITION COMPRISING BETWEEN ABOUT 80 AND ABOUT 99.5 WEIGHT PERCENT, BASED ON COMPOSITION WEIGHT, OF (A) A POLYMERIZED ETHYLENICALLY UNSATURATED MONOMERIC MATERIAL CONTAINING AT LEAST ABOUT 80 WEIGHT PERCENT OF POLYMERIZED ACRYLONITRILE, AND (B) BETWEEN ABOUT 20 AND ABOUT 0.5 WEIGHT PERCENT, BASED ON COMPOSITION WEIGHT, OF A GRAFT COMPOLYMER OF (A) FROM ABOUT 10 TO ABOUT 90 WEIGHT PERCENT, BASED ON GRAFT COPOLYMER WEIGHT, OF A MIXTURE OF MONOMERS CONSISTING OF (1) FROM ABOUT 10 TO ABOUT 90 MOLE PERCENT OF AN ACRYLATE MONOMER OF THE FORMULA: 